JP2541808B2 - Solid catalyst component for olefin polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention has a high activity when subjected to the polymerization of olephins, and is capable of obtaining a stereoregular polymer in a high yield. It relates to a performance solid catalyst component. More specifically, the present invention relates to a substance obtained by reacting metal magnesium powder with chloride of an aliphatic hydrocarbon that is liquid at room temperature in the presence of iodine in the absence of a solvent, a diester of phthalic acid, Co-ground with titanium tetrachloride and dialkoxymagnesium at a low temperature, and the obtained product is obtained by contacting with titanium tetrachloride in the presence of aromatic hydrocarbon or aromatic halogenated hydrocarbon which is liquid at room temperature. The present invention relates to a solid catalyst component for olefin polymerization.

[Prior art]

Recently, as a catalyst for the polymerization of olefins such as propylene, in place of the conventionally known catalyst component of titanium trichloride, many new types of catalysts in which titanium, which is an active component, is supported on magnesium chloride together with an electron donor have been developed. Proposed.

The earliest of these was developed by co-milling a complex of an organic monocarboxylic acid ester as an electron donor and titanium tetrachloride with magnesium chloride, or an organic monocarboxylic acid as an electron donor. There is a product obtained by treating a co-ground product of an acid ester and magnesium chloride with titanium tetrachloride.

However, they cannot be said to have satisfactory properties for use on an industrial scale, and those which improve various properties, for example, diethoxymagnesium instead of magnesium chloride, and special electron donors are used. Various proposals have been made for those using a compound, or those obtained by modifying the combination method of the above-mentioned substances, the contact means and the like.

For example, in JP-A-54-94590, a catalyst component is prepared by using magnesium dihalide as a starting material, and an organoaluminum compound, an organic carboxylic acid ester and M
A method of combining a compound having a —O—R group and the like for use in the polymerization of olefins is disclosed, and JP-A-57-
In 63310, various catalysts as electron donors, magnesium chloride in active form, and a titanium compound are combined to prepare a catalyst component, and further Si—O bond or Si—
A method for polymerizing propylene using a compound having an N bond and an organoaluminum compound is disclosed.

[Problems to be solved by the invention]

In the prior art, chlorine contained in magnesium chloride, which occupies the main stream as a carrier material, has a drawback that it adversely affects the produced polymer, like the halogen element in titanium halides. On the other hand, it is required that the activity of chlorine be substantially negligible, or that the concentration of magnesium chloride itself be kept low.

Further, when a catalyst component having the above magnesium chloride as a carrier is used in combination with an organoaluminum compound to polymerize olefins, particularly when stereoregular polymerization of propylene, 1-butene, etc. is carried out industrially, when carrying out the polymerization reaction. It is essential to use an organic monocarboxylic acid ester as an electron donor. However, in this case, it is necessary to use an extremely large amount of organic monocarboxylic acid ester, and as a result, there has been a problem that a peculiar ester odor is imparted to the produced polymer.

Furthermore, in so-called highly active supported catalysts such as catalysts using a catalyst component having magnesium chloride as a carrier, the activity at the initial stage of polymerization is high, but deactivation with time is large and it becomes a problem in process operation, and block copolymerization It was virtually impossible to use it if the polymerization time was longer.

JP-A-54-94590 has been proposed to improve this point, but as is clear from the description of the publication, in this case, an organic carboxylic acid ester is used both during catalyst preparation and during polymerization. Is needed.
Generally, the organic carboxylic acid ester contained in the catalyst is
By treatment with titanium halide or washing with an organic solvent, the amount of odor of the produced polymer is negligible. However, the organic carboxylic acid ester used during the polymerization is extremely large amount as compared with the amount contained in the catalyst as described above, and when the polymerization is carried out in a liquid or gaseous monomer, almost all of it is At present, it is contained in the produced polymer, and accordingly,
It can be said that the problem of the odor of the produced polymer cannot be solved as long as the organic carboxylic acid ester is used during the polymerization. Further, the method disclosed in the publication, as seen from the examples, requires extremely complicated operations and the obtained catalyst is practically sufficient in terms of both performance and active connectivity. That is not the case.

The present inventors have conducted extensive studies to solve various problems in the conventional art, and succeeded in providing a novel solid catalyst component for polymerization of olephins to Mushroom.

[Disclosure of Invention]

The present invention is a substance (a) obtained by reacting a magnesium metal powder with a chloride of an aliphatic hydrocarbon that is liquid at a room temperature of not less than 2 times in the presence of iodine in the absence of a solvent.
Phthalic acid diester (b) and titanium tetrachloride (c)
And a product obtained by co-grinding with dialkoxymagnesium (d) at a low temperature of 10 ° C. or lower, in the presence of aromatic hydrocarbon or aromatic halogenated hydrocarbon (e) which is liquid at room temperature, It provides a solid catalyst component obtained by contacting with titanium chloride (c).

In order to obtain a substance (hereinafter simply referred to as substance (a)) obtained by the reaction of the above-mentioned (a) metallic magnesium powder with chloride of an aliphatic hydrocarbon which is liquid at room temperature in the present invention, commercially available metallic magnesium is used. The powder and the chloride of the aliphatic hydrocarbon that is liquid at room temperature are reacted in the presence of iodine in the absence of an organic solvent, and the chloride of the aliphatic hydrocarbon that is liquid at room temperature is metallic magnesium powder. It is necessary to use 2 mol or more per 1 mol. Further, the reaction temperature and the reaction time are arbitrary as long as the above reaction proceeds sufficiently and are not particularly limited, but usually 10 ° C. or higher at 10 ° C. or higher.
It is carried out for at least 30 minutes and preferably at 40 ° C. for at least 30 minutes. This reaction is a Grineer type reaction, and the absorption of an alkyl group is observed when the IR spectrum of the substance (a) obtained by the reaction is measured.

Examples of chlorides of aliphatic hydrocarbons that are liquid at room temperature and are used in the production of the substance (a) include, for example, n-propyl chloride, isopropyl chloride, n-butyl chloride, isobutyl chloride, pentyl chloride, hexyl chloride and octyl chloride. Can be given.

Examples of the (b) phthalic acid diester (hereinafter simply referred to as (b) substance) in the present invention include dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate. , Ethyl butyl phthalate, ethyl isobutyl phthalate, ethyl propyl phthalate and the like can be mentioned as examples.

Examples of the dialkoxymagnesium (d) in the present invention (hereinafter simply referred to as the substance (d)) include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dipentoxymagnesium and the like.

In the present invention, the aromatic hydrocarbon or aromatic halogenated hydrocarbon which is liquid at room temperature (e) (hereinafter simply referred to as (e)
Examples of the substance) include toluene, xylene,
And aromatic halogenated hydrocarbons such as chlorobenzene, o-dichlorobenzene and bromobenzene.

When obtaining the solid catalyst component in the present invention, the use ratio of each raw material constituting the solid catalyst component is arbitrary and is not particularly limited as long as it does not adversely affect the performance of the produced solid catalyst component. However, the amount of the (b) substance is usually 0.01 to 1 g, relative to 1 g of the (a) substance,
The substance (a) is in the range of 0.1 to 2 g. Regarding the titanium tetrachloride, when co-milling with the substances (a), (b) and (d) at a low temperature, 1 g of the (a) substance is used.
On the other hand, it is in the range of 0.01 to 1 g, and when brought into contact with the product obtained by the co-milling, it is in the range of 0.1 g or more, preferably 1 g or more. The amount of the substance (e) coexisted at the time of this contact is in the range of 0.01 to 100 ml, preferably 0.1 to 10 ml, per 1 ml of titanium tetrachloride.

Substance (a), substance (b), titanium tetrachloride (c)
The co-milling of substances (d) and (d) is below 10 ° C, preferably 0
It is carried out at a low temperature of 0 ° C. or lower for usually 10 minutes or longer, preferably 30 minutes or longer.

When the product obtained by the above co-milling is contacted with titanium tetrachloride in the presence of substance (e), it is usually -10
Temperature range from ℃ to the boiling point of titanium tetrachloride for 10 minutes ~
It is preferable to perform the treatment for about 100 hours. After this contact, titanium tetrachloride can be repeatedly contacted with the obtained product. In that contact, the substance (e) may or may not be allowed to coexist. The product thus obtained may optionally be washed with an organic catalyst such as n-heptane.

All of these aspects are included in one aspect in the practice of the present invention.

The series of operations for preparing the solid catalyst component in the present invention is preferably carried out in the absence of oxygen and water.

The solid catalyst component prepared as described above is combined with an organoaluminum compound to form a catalyst for olefin polymerization, and at this time, if necessary, a third component such as a piperidine derivative or an oxygen-containing organosilicon compound may be added. It is possible to coexist.

The polymerization reaction using the catalyst for polymerization according to the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer used can be used in either gas or liquid state. it can. Polymerization temperature is 20
0 ℃ or less, preferably 100 ℃ or less, the polymerization pressure is 100kg /
cm ² · G or less, preferably 50 kg / cm ² · G or less.

The olefins homopolymerized or copolymerized by using the olefin polymerization catalyst according to the present invention are ethylene, propylene, 1-butene and the like.

〔The invention's effect〕

The solid catalyst component for polymerization of olefins according to the present invention, when used for the polymerization of olefins, shows a high activity which is unpredictable in the past, and therefore the amount of catalyst residue present in the produced polymer. Can be controlled to an extremely low level, and since the residual chlorine is extremely small, the effect of chlorine on the product can be reduced to the extent that no deashing step is required.

Since chlorine remaining in the produced polymer causes corrosion of equipment used in steps such as granulation and molding, it also causes deterioration of the produced polymer itself, yellowing, etc. Obtaining is of great benefit to the art.

Further, according to the solid catalyst component of the present invention, by not adding the organic carboxylic acid ester at the time of polymerization, it is possible to solve a big problem that an ester odor adheres to the produced polymer.

Furthermore, conventionally, there was a common drawback in so-called highly active supported catalysts, in which the activity per unit time of the catalyst was significantly reduced with the progress of polymerization, but in the catalyst according to the present invention, Since the decrease in activity with the passage of time is extremely small compared to conventionally known catalysts, it is also useful when prolonging the polymerization time such as copolymerization, and when a higher polymerization pressure is adopted. Because of the large increase in the activity in, it can be widely used in bulk polymerization and gas phase polymerization, which have recently received attention.

Moreover, according to the solid catalyst component of the present invention, a polymer having a high degree of stereoregularity can be obtained.

In addition, in the industrial production of olefin polymers, coexistence of hydrogen at the time of polymerization is generally considered from the viewpoint of MI control and the like, but conventional magnesium chloride is used as a carrier and organic carboxylic acid ester is used. The catalyst had a drawback that its activity and stereoregularity were significantly reduced in the presence of hydrogen. However, when the polymerization of olefin is carried out in the presence of hydrogen using the solid catalyst component according to the present invention, even when the MI of the produced polymer is extremely high,
The activity and stereoregularity are not reduced. Such an effect has been strongly desired by those skilled in the art. Further, in the industrial production of polyolefin, the bulk specific gravity of the produced polymer becomes a very big problem in terms of the ability of the polymerization apparatus, the ability of the post-treatment step, etc., but the solid catalyst component according to the present invention has this point. Also has extremely excellent characteristics.

[Examples and Comparative Examples]

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

Example 1 (1) (a) Preparation of Material Using a round bottom flask with a volume of 2.0 equipped with a stirrer,
After thoroughly replacing it with nitrogen gas, 30 g of magnesium metal powder, 1.0 g of iodine and 1.2 g of n-butyl chloride were added.
And reacted at the boiling point of n-butyl chloride for 5 hours. After the reaction was completed, the supernatant was removed and the product was added to 500 ml.
After being washed with n-butyl chloride for 3 times, it was dried under reduced pressure to obtain a powdery substance.

(2) Preparation of solid catalyst component 20 g of the powdery substance obtained in (1) above, 7.5 ml of dibutyl phthalate, 4.0 ml of TiCl ₄ and 5.0 g of diethoxymagnesium were used under a nitrogen gas atmosphere to make a total volume of 25 mmφ stainless steel balls. It was charged into a vibrating millpot with a capacity of 4/5 and a capacity of 1.0, and co-milling was performed at a frequency of 1430 v.pm and an amplitude of 3.5 mm for 17 hours in a temperature atmosphere of -15 ° C.

Using a round bottom flask with a capacity of 500 ml equipped with a stirrer,
After sufficiently replacing with nitrogen gas, 5 g of the solid composition obtained by the co-milling treatment was taken into it, and TiCl ₄ 50 m
1 and 50 ml of toluene were added, and the temperature was raised to 115 ° C. to react for 2 hours. After completion of the reaction, the supernatant was removed, and 50 ml of TiCl ₄ and 50 ml of toluene were newly added to the product, and the mixture was reacted at 115 ° C. for 2 hours. After the reaction is completed, the product is cooled to 40 ° C.
-Washing with 200 ml heptane 10 times gave a solid catalyst component.

At this time, the titanium content in the solid catalyst component was measured and found to be 2.48% by weight.

(3) Polymerization of propylene Using an autoclave equipped with a stirrer and having an inner volume of 2.0, the autoclave was completely replaced with nitrogen gas, and then 190 mg of triethylaluminum, 23 mg of 2,2,6,6-tetramethylpiperidine and the solid catalyst component of 3.0 Charged mg. Then, hydrogen gas 1.8 and liquefied propylene 1.4 were charged and the polymerization reaction was carried out at 70 ° C. for 1 hour. After the completion of the polymerization reaction, the produced polymer is dried under reduced pressure at 80 ° C., and the amount of the obtained product is designated as (A). Further, this product was extracted with boiling n-heptane for 6 hours to obtain a polymer insoluble in n-heptane, and the amount of this product is designated as (B).

The polymerization activity (C) per the solid catalyst component used is represented by the following formula.

The yield (D) of all crystalline polymer is represented by the following formula.

Further, the residual chlorine content in the produced polymer is represented by (E), the MI of the produced polymer is represented by (F), and the bulk specific gravity is represented by (G). The obtained results are shown in Table 1.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the polymerization time was 30 minutes. The obtained results are as shown in Table 1.

Example 3 An experiment was carried out in the same manner as in Example 1 except that the polymerization reaction was carried out by the following method.

700 ml of n-heptane was charged into an autoclave with an internal volume of 2.0, which was completely replaced with nitrogen gas, and 301 m of triethylaluminum was added while maintaining a nitrogen gas atmosphere.
g, 2,2,6,6-tetramethylpiperidine 37 mg, and then 10.0 mg of the solid catalyst component prepared by the method of Example 1 were charged.
After that, 150 ml of hydrogen gas was charged, the temperature was raised to 70 ° C, and propylene gas was introduced, while maintaining a pressure of 6 kg / cm ² · G.
The polymerization reaction was performed for a time. After the completion of the polymerization reaction, the obtained solid polymer was separated, heated to 80 ° C., and dried under reduced pressure. On the other hand, the amount of the polymer dissolved in the polymerization solvent by condensing the liquid is defined as (H), and the amount of the solid polymer is defined as (I). Further, the obtained solid polymer was extracted with boiling n-heptane for 6 hours,
A polymer insoluble in n-heptane was obtained, and this amount is designated as (J).

The polymerization activity (K) per solid catalyst component is represented by the following formula.

Further, the yield (L) of the crystalline polymer is represented by the following formula, The yield (M) of the whole crystalline polymer is determined by the following equation.

Further, residual chlorine in the produced polymer is represented by (N), MI of the produced polymer is represented by (O), and bulk specific gravity is represented by (P). The results obtained are shown in Table 2.

Example 4 An experiment was performed in the same manner as in Example 3, except that the polymerization time was changed to 2 hours. The results obtained are shown in Table 2.

Example 5 An experiment was conducted in the same manner as in Example 1 except that the same amount of dipropyl phthalate was used instead of dibutyl phthalate. The titanium content in the solid catalyst component at this time is 2.
It was 18% by weight. An experiment was conducted in the same manner as in Example 1 during the polymerization. The results obtained are as shown in Table 1.

Line preparation of the solid catalyst component in the same manner except for the use dipropyl phthalate 5.0ml and TiCl ₄ 2.0 ml instead of Example 6 dibutyl phthalate 7.5ml and TiCl ₄ 4.0 ml Example 1 Natsuta. The titanium content in the solid catalyst component at this time is 2.
It was 31% by weight. An experiment was conducted in the same manner as in Example 1 during the polymerization. The results obtained are as shown in Table 1.

Comparative Example 1. 20 g of commercially available MgCl ₂ and 5.0 ml of dibutyl phthalate are pulverized under the same conditions as in Example 1. Then, 5 g of the pulverized composition was charged into a glass vessel having an internal volume of 500 ml under a nitrogen gas atmosphere, 200 ml of TiCl ₄ was added, and a stirring reaction was carried out at 120 ° C. for 2 hours. After completion of the reaction, the supernatant was removed, 200 ml of TiCl ₄ was newly added, and the reaction was carried out at 120 ° C for 2 hours.

After completion of the reaction, it was cooled to 40 ° C. and washed 10 times with 200 ml of n-heptane to obtain a solid catalyst component. At this time, the titanium content in the solid catalyst component was measured and found to be 1.64% by weight.

An experiment was conducted in the same manner as in Example 1 except that 6.0 mg of the above solid catalyst component was used for the polymerization. The results obtained are as shown in Table 1.

Comparative Example 2. An experiment was conducted in the same manner as Comparative Example 1 except that the polymerization time was 30 minutes. The results obtained are as shown in Table 1.

Comparative Example 3. An experiment was performed in the same manner as in Comparative Example 1 except that the polymerization reaction was performed in the same manner as in Example 3. The results obtained are shown in Table 2.

As is clear from comparison between Examples 1 and 2 and Comparative Examples 1 and 2, the catalyst according to the present invention has an extremely small decrease in activity with the passage of polymerization time.

As is clear from comparison between Examples 1 and 3 and Comparative Examples 1 and 3, the catalyst according to the present invention shows a large increase in activity when a higher polymerization pressure is adopted.

[Brief description of drawings]

FIG. 1 is a schematic drawing for helping understanding of the present invention.

Claims (1)

(57) [Claims] 1. A substance (a) obtained by reacting a magnesium metal powder with a chloride of an aliphatic hydrocarbon which is more than twice the molar amount and is liquid at room temperature in the presence of iodine in the absence of a solvent,
A product obtained by co-grinding phthalic acid diester (b), titanium tetrachloride (c) and dialkoxymagnesium (d) at a low temperature of 10 ° C. or lower is used as an aromatic hydrocarbon or aromatic halogen which is liquid at ordinary temperature. In the presence of a modified hydrocarbon (e),
Further, a solid catalyst component for olefin polymerization, which is obtained by contacting with the titanium tetrachloride (c).